US4645307A - Electrochromic device - Google Patents

Electrochromic device Download PDF

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US4645307A
US4645307A US06/662,563 US66256384A US4645307A US 4645307 A US4645307 A US 4645307A US 66256384 A US66256384 A US 66256384A US 4645307 A US4645307 A US 4645307A
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electrochromic
color
prussian blue
layers
electrode
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Takeshi Miyamoto
Mikio Ura
Shigenori Kazama
Takao Kase
Yoshiko Maeda
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Nissan Motor Co Ltd
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Nissan Motor Co Ltd
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Assigned to NISSAN MOTOR CO., LTD. reassignment NISSAN MOTOR CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: KASE, TAKAO, KAZAMA, SHIGENORI, MAEDA, YOSHIKO, MIYAMOTO, TAKESHI, URA, MIKIO
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1516—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
    • G02F2001/1517—Cyano complex compounds, e.g. Prussian blue

Definitions

  • This invention relates to an electrochromic device using an electrochromic material which can alternately and stably exist in three different oxidation states and assumes different colors in the respective oxidation states.
  • a typical example of the electrochromic material is Prussian blue.
  • a solid inorganic oxide film deposited on a transparent electrode serves as an electrochromic material.
  • the electrochromic oxide film is colorless in its normal state and assumes a blue color when a negative potential is applied to the electrode in contact with the oxide film.
  • Prussian blue has attracted interest mainly because it can easily be formed as a film by an electrodeposition process and, therefore, would be favorable for the manufacture of relatively large-sized electrochromic display devices. Prussian blue loses its characteristic blue color when electrochemically reduced to such an extent that the trivalent iron in its crystal lattice entirely turns into divalent iron.
  • the blue color changes into light yellow when the entire iron in the crystal lattice of Prussian blue is oxidized to trivalent iron.
  • oxidation of a Prussian blue film in the presence of an electrolyte causes gradual decomposition of the Prussian blue film. Therefore, it is difficult to practically utilize the blue-to-yellow and reverse changes in the color of Prussian blue.
  • This invention provides an electrochromic device which comprises a first electrode layer which is transparent, a second electrode layer arranged opposite to and spaced from the first electrode layer, a first electrochromic layer formed on the first electrode layer on the side facing the second electrode layer, a second electrochromic layer formed on the second electrode layer on the side facing the first electrode layer and an electrolyte which fills up the gap between the first and second electrochromic layers, and the primary feature of the invention resides in that the first and second electrochromic layers are both formed of an electrochromic material which undergoes electrochemical oxidation and reduction in two stages and can alternately and stably assume three different oxidation states, the color of the electrochromic material in each oxidation state being different from the colors in the other two oxidation states such that there is a clear contrast between the color in the intermediate oxidation state and a composite color given by superposition of the color in the highest oxidation state on the color in the lowest oxidation state.
  • the same electrochromic material is used for the first and second electrochromic layers.
  • This electrochromic device normally exhibits the color of the employed electrochromic material in its intermediate oxidation state.
  • the color of the device changes to a composite color given by superposition of the color of one electrochromic layer which is oxidized to the highest oxidation state and the color of the other electrochromic layer which is reduced to the lowest oxidation state.
  • This color change occurs irrespective of the polarity of the applied voltage, and this is an important advantage of the present invention.
  • Preferred examples of the above defined electrochromic material are Prussian blue and 2,2'-bipyridyl iron complex.
  • the first and second electrochromic layers are formed of Prussian blue the aforementioned composite color becomes light yellow in contrast with the blue color of Prussian blue in the normal state.
  • the two electrochromic layers are formed of 2,2'-bipyridyl iron complex which assumes red color in its normal state, the composite color becomes light blue.
  • the electrolyte in the device be a solution of an alkali metal salt which serves as a supporting electrolyte, such as lithium perchlorate, in an organic polar solvent such as propylene carbonate containing 0.8-1.5 wt % of water or, alternatively, that the electrochromic layer(s) of Prussian blue be pretreated such that the Fe 3+ ion interstitially existing in the crystal lattice of Prussian blue is substituted by alkali metal cation.
  • the electrolyte in the device is a solution of an alkali metal salt in an organic polar solvent which need not contain water.
  • Prussian blue as the preferred electrochromic material in this invention can easily be formed by a known electrodeposition process. Therefore, a relatively large-sized device according to the invention can easily be produced at relatively low cost.
  • FIG. 1 is a schematic and sectional view of an electrochromic display device according to the invention.
  • FIG. 2 shows a steric structure of Prussian blue, which is a preferred electrochromic material in the present invention
  • FIG. 3 is a schematic and sectional view of an electrolytic cell used in our experiment on the electrochromic properties of Prussian blue:
  • FIG. 4 is a diagram showing a cyclic voltamogram on the indicator electrode coated with a film of Prussian blue in the cell of FIG. 3, the cell using an aqueous solution as the electrolyte;
  • FIG. 5 is a diagram showing a cyclic voltamogram on the same indicator electrode observed when a solution of a sodium salt in propylene carbonate was used as the electrolyte;
  • FIGS. 6 to 11 show variations of the voltamogram of FIG. 5 observed when water was added to the electrolyte in gradually increasing amounts.
  • FIG. 12 shows a variation of the cyclic voltamogram of FIG. 5 observed when the indicator electrode was subjected to electrochemical oxidation and reduction in a water-containing electrolyte before testing in the non-aqueous electrolyte.
  • FIG. 1 shows a general construction of an electrochromic display device according to the invention.
  • the device has top and bottom substrates 10 and 20 which are made of a transparent material such as glass plate.
  • a transparent electrode 12 in the form of a film is deposited on the inside surface of the top substrate 10, and a first electrochromic layer 14 is formed on the transparent electrode 12 in a desired pattern.
  • Another transparent electrode 22 in the form of a film is deposited on the inside surface of the bottom substrate 20, and a second electrochromic layer 24 is formed on this electrode 22 in a desired pattern.
  • the material of the two electrodes 12, 14 is tin dioxide or diindium trioxide
  • the material of the first and second electrochromic layers 14, 24 is Prussian blue.
  • the two substrates 10 and 20 are held spaced from each other by a sealing resin 16 such that the first and second electrochromic layers 14 and 24 are opposite to and spaced from each other.
  • the space defined by the two substrates 10, 20 and the peripheral seal 16 is filled with a liquid electrolyte 18, which is a solution of an alkali metal salt such as lithium perchlorate in an organic polar solvent such as propylene carbonate.
  • this complex is a composite valence complex which has a fundamental crystal lattice constructed by bridging Fe(III) and Fe(II) by cyanogen groups and includes Fe 3+ ions or alkali metal ions such as Li + , Na + , K + or Pb + ions as interstitial ions (not shown in FIG. 2).
  • This complex is called insoluble Prussian blue Fe(III)[Fe(III)Fe(II)(CN) 6 ] 3 when the interstitially existing ions are Fe 3+ ions and soluble Prussian blue MFe(III)Fe(II)(CN) 6 , where M is Li, Na, K or Pb, when the interstitially existing ions are alkali metal ions.
  • the soluble Prussian blue does not actually dissolve in water: it is called “soluble” because it gives a colloidal dispersion without precipitating.
  • a film of Prussian blue can be formed on an electrode surface by an electrodeposition process using a mixed solution containing Fe 3+ ions and hexacyanoferrate(III) ions [Fe(CN) 6 ] 3- . Electrolysis of the mixed solution results in the deposition of Prussian blue on the surface of the cathode as an electrochemical reduction product in the form of film tightly adhering to the cathode surface.
  • FIG. 3 shows an electrolytic cell used in the experiment.
  • An indicator electrode 32 was prepared by coating an indium trioxide electrode having a surface area of 1 cm 2 with a film of Prussian blue.
  • the electrolyte liquid 38 was an aqueous solution of potassium chloride (1 N). Nitrogen gas was introduced into the cell to expel air (oxygen) therefrom, and the respective electrodes 32, 34, 36 were connected to a potentiostat (not shown) used as a power supply.
  • FIG. 4 is a cyclic voltamogram showing the relationship between the potential at the indicator electrode 32 (on the basis of the SCE potential) and the electrolysis current found by the experiment. Initially, the potential at the Prussian blue indicator electrode 32 was on the level of about +0.5 V, and the electrode surface assumed blue color.
  • the externally applied voltage was varied so as to cause the indicator electrode potential (on the basis of the SCE potential) to continuously vary in the directions indicated by arrows in FIG. 4. While the indicator potential was varying toward the positive side a peak of electrolytic oxidation current appeared at a potential of about +0.3 V and another peak at about +0.95 V. While the potential was varying toward the negative side a peak of electrolytic reduction current appeared at a potential of about +0.85 V and another peak at about +0.15 V.
  • the indicator electrode 32 assumed blue color while the indicator electrode potential was in the range (A) in FIG. 4. In the range (B) the indicator electrode 32 was colorless and transparent. In the range (C) the indicator electrode 32 assumed a light yellow color.
  • the curve in solid line represents the voltamogram at the first cycle.
  • the indicator electrode potential was continuously varied within the range between -0.3 V and +0.5 V to repeat only the processes L 1 and L 2 , it was possible to stably repeat the blue-to-colorless and reverse changes in the color of the indicator electrode 32.
  • the indicator electrode potential was continuously varied over the range between -0.3 V and +1.15 V to repeat not only the processes L 1 and L 2 but also the processes L 3 and L 4 , the electrolytic oxidation and reduction currents decreased gradually.
  • the current peaks reduced as represented by the curve in dotted line and by the curve in chain line, respectively.
  • the cyclic change in the indicator electrode potential was repeated tens of times.
  • the shape of the potential-current curve varied little by little from the shape shown in FIG. 10 to the shape shown in FIG. 11.
  • the shape of the curve scarcely varied even though the cyclic change in the potential was repeated thousands of times, and it was possible to stably repeat the changes in the color of the Prussian blue indicator electrode between the colorless transparency at potentials near to -0.3 V, blue color at potentials near to +0.5 V and the light and transparent yellow color at potentials near to +1.3 V.
  • the stable voltamogram of FIG. 11 was obtained also when the indicator electrode subjected to tens of cycles of the potential change was tested in the electrolyte liquid containing 0.8 wt % or 1.8 wt % of water.
  • the experiment was extended by increasing the content of water in the solution of sodium perchlorate in propylene carbonate.
  • the result of the measurement was still as shown in FIG. 11 until the water content reached about 15 wt %.
  • the water content exceeded 15 wt %, gradual decomposition of the Prussian blue in the oxidized state took place in the same manner as in the case of using a purely aqueous solution as the electrolyte liquid.
  • the above presumption is supported by experimental results.
  • the Prussian blue electrode 32 on which the voltamogram of FIG. 11 was obtained after repeating the potential change tens of times in the sodium perchlorate solution in propylene carbonate containing 4.6 wt % of water was used in an additional experiment. That is, the water-containing electrolyte solution was replaced by the 1 N sodium perchlorate solution in the refined propylene carbonate, and the indicator electrode potential was continuously varied in the manner as shown in FIG. 5. In this case the voltamogram was as shown in FIG. 12. Unlike the voltamogram of FIG. 5, a peak of electrolytic oxidation current appeared at the potential of about +1.0 V, and at this stage the color of the indicator electrode changed from blue to yellow. When the potential was varied in the reverse direction a peak of reduction current appeared at about +0.75 V, and the yellow color of the indicator electrode reverted to blue.
  • an aqueous solution of potassium chloride was first used as the electrolyte liquid 38 in the experimental cell of FIG. 3, and the indicator electrode potential was continuously and cyclically varied over the range from +0.5 V to -0.4 V wherein Prussian blue is chemically stable. The potential change was repeated twenty times. After that the same indicator electrode was tested in 1 N solution of sodium perchlorate in refined propylene carbonate without adding water thereto. Also in this case the voltamogram was as shown in FIG. 12.
  • such a pretreatment can be accomplished by subjecting the electrodeposited Prussian blue film to electrochemical oxidation and reduction reactions in an electrolyte liquid prepared by dissolving a supporting electrolyte of which the cation is alkali metal ion in either water or an organic solvent containing at least 15 wt % of water until the Prussian blue film undergoes at least one cycle of the blue-to-colorless and reverse changes in color, while limiting the potential at the Prussian blue electrode within a range wherein the Prussian blue film does not decompose.
  • a pretreatment of the same effect can be accomplished by subjecting the Prussian blue film to electrochemical oxidation and reduction reactions in an electrolyte liquid prepared by dissolving a supporting electrolyte of which the cation is alkali metal ion in an organic polar solvent containing 0.8-15 wt % of water until the Prussian blue film undergoes at least one cycle of the blue-to-colorless and reverse changes and/or at least one cycle of the blue-to-yellow and reverse changes in color, while limiting the potential at the Prussian blue electrode within a range wherein the Prussian blue film does not decompose.
  • the electrochromic material in the present invention is not limited to Prussian blue.
  • materials which also undergo electrochemical oxidation and reduction in two stages stably and repeatedly and can alternately assume three different oxidation states with such changes in color that there is a clear contrast between the color in the intermediate oxidation state and a composite color given by superposition of the color in the highest oxidation state on the color in the lowest oxidation state, and such materials are of use as the material of the first and second electrochromic layers 14 and 24 in the device of FIG. 1.
  • 2,2'-bipyridyl iron complex is fully practicable.
  • organic solvent in the electrolyte liquid it is preferable to select a solvent which is highly polar, can dissolve popular supporting electrolytes in high concentrations and does not undergo electrochemical oxidation or reduction within the potential range utilized in the electrochromic device.
  • a solvent which is highly polar can dissolve popular supporting electrolytes in high concentrations and does not undergo electrochemical oxidation or reduction within the potential range utilized in the electrochromic device.
  • Propylene carbonate and acetonitrile are named as preferred examples.
  • An electrochromic display device of the construction shown in FIG. 1 was produced in the following way.
  • a transparent glass plate was used as the material of the top and bottom substrates 10 and 20, and the transparent electrodes 12 and 22 were formed respectively on the two substrates 10 and 20 by vacuum deposition of tin dioxide. Prussian blue was electrodeposited on the first electrode 12 to a thickness of 2000 ⁇ to thereby form the first electrochromic layer 14, and also on the second electrode 22 to the same thickness to thereby form the second electrochromic layer 24.
  • Each of the thus processed substrates 10 and 20 was immersed in 1 mole/liter solution of potassium chloride in water in combination with a counter electrode formed of platinum plate and a saturated calomel reference electrode, and a variable voltage was applied to the electrode 12 or 22 covered with Prussian blue 14, 24 so as to continuously vary the potential at this electrode 12 or 22 over the range from -0.4 V to +0.5 V on the basis of the SCE potential. In this manner the pretreatment of the Prussian blue layers 14, 24 was accomplished.
  • the two substrates 10 and 20 were arranged opposite to each other and assembled into a blank cell by application of an epoxy sealant 16 therebetween so as to surround the electrochromic layers 14, 24.
  • an opening (not shown) left in the peripheral seal 16 1 mole/liter solution of lithium perchlorate in propylene carbonate was introduced into the cell as the electrolyte liquid 18, and the aforementioned opening was completely sealed to thereby complete the electrochromic device.
  • both the first and second Prussian blue layers 14 and 24 in the thus produced device assumed blue color.
  • a voltage of 1.2-1.4 V was applied across the two electrodes 12 and 22, the Prussian blue layer on the negative side was electrochemically reduced to the lowest oxidation state and became colorless and transparent, whereas the Prussian blue layer on the positive side was oxidized to the highest oxidation state and assumed a light yellow color.
  • the color of the entire device or the composite color of the two Purssian blue layers 14, 24 changed from the initial blue color of about 10% transmittance to a light yellow color of about 60% transmittance.
  • both the first and second Prussian blue layers 14 and 24 again assumed the blue color.
  • the first and second electrochromic layers 14 and 24 are formed of the same Prussian blue. In principle, therefore, there is no need of paying attention to the polarity of voltage applied to the device to effect bleaching. In practice, however, it is favorable to alternate the polarity of that voltage in repeating bleaching many times because the life of the device can be prolonged by doing so.
  • the device of FIG. 1 was produced generally in accordance with Example 1 except that the pretreatment of the Prussian blue layers in the aqueous solution was omitted and that 1 mole/liter solution of sodium perchlorate in acetonitrile containing 5.0 wt % of water was used as the electrolyte liquid 18.
  • a voltage applied across the two electrodes over the range from 0 V to +1.4 V, it was possible to stably repeat the blue-to-light yellow and reverse color changes.
  • the solvent of the electrolyte was changed to propylene carbonate containing 5 wt % of water, and the supporting electrolyte was changed to lithium perchlorate in one case and to potassium borofluoride in the other case. In every case the electrochromic function of the device was unchanged.
  • 2,2'-bipyridyl iron complex was used as the material of the first and second electrochromic layers 14 and 24, and 1 mole/liter solution of sodium perchlorate in propylene carbonate was used as the electrolyte liquid 18. Otherwise the manufacturing process was as described in Example 2.
  • the 2,2'-bipyridyl iron complex layers 14 and 24 in this device assumed a red color.
  • a voltage of 2.5 V was applied across the two electrodes, one of the two electrochromic layers 14, 24 was electrochemically reduced to assume a blue color whereas the other was oxidized to assume a white color. Accordingly the color of the entire device became light blue as a composite color of the respectively reduced and oxidized 2,2'-bipyridyl iron complex layers 14 and 24.
  • the bottom substrate 20 and the second electrode 22 need not be transparent.
  • the intermediate green color can also be utilized.
  • the device By open-circuiting the device while the device is assuming green color in the course of the color change from blue to light yellow or reversely, it is possible to keep the green color unchanged. Accordingly, it is possible to produce a multicolor electrochromic device which can alternately assume blue, green and light yellow colors.

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
US06/662,563 1983-10-20 1984-10-19 Electrochromic device Expired - Fee Related US4645307A (en)

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JP58-195176 1983-10-20
JP58195176A JPS6087316A (ja) 1983-10-20 1983-10-20 エレクトロクロミツク素子

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US4726664A (en) * 1985-03-25 1988-02-23 Nippon Sheet Glass Co., Ltd. Electrochromic device
US4750816A (en) * 1985-05-01 1988-06-14 Toyoda Gosei Co., Ltd. Electrochromic element comprising an organic, oxidative color-forming layer and an inorganic, reductive color-forming layer
US4784477A (en) * 1986-07-22 1988-11-15 Nissan Motor Co., Ltd. Electrochromic device using transition metal oxide and method of producing same
US4960323A (en) * 1988-10-05 1990-10-02 Ford Motor Company Method for maintaining the electrochromic activity of an electrochromic material
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US5457564A (en) * 1990-02-26 1995-10-10 Molecular Displays, Inc. Complementary surface confined polymer electrochromic materials, systems, and methods of fabrication therefor
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US5774255A (en) * 1996-09-23 1998-06-30 Mcdonnell Douglas Corporation Adaptive infrared modulator
US5818636A (en) * 1990-02-26 1998-10-06 Molecular Displays, Inc. Complementary surface confined polmer electrochromic materials, systems, and methods of fabrication therefor
US6246508B1 (en) * 1996-08-08 2001-06-12 Danionics A/S High voltage electrochromic device
KR100392977B1 (ko) * 1994-11-11 2003-10-23 소니 가부시끼 가이샤 광학장치
US20050237594A1 (en) * 2004-04-26 2005-10-27 Kuo-Chuan Ho Electrochromic device using poly(3,4-ethylenedioxythiophene) and derivatives thereof
CN102103297A (zh) * 2011-01-14 2011-06-22 天津大学 自褪色节能电致变色器件的制备方法
KR20110106622A (ko) * 2010-03-23 2011-09-29 삼성전자주식회사 전기 변색 물질 및 이를 포함하는 전기 변색 소자
CN112305829A (zh) * 2020-11-13 2021-02-02 烟台大学 一种电致变色玻璃器件、其制备方法及应用
CN112534344A (zh) * 2018-03-16 2021-03-19 国立研究开发法人物质·材料研究机构 金属配合物系电致变色器件
CN113495392A (zh) * 2020-04-01 2021-10-12 深圳市光羿科技有限公司 一种电致变色器件及其变色方法
US11513410B2 (en) * 2017-05-10 2022-11-29 National Institute For Materials Science Electrochromic device using organic/metal hybrid polymer and method for producing same

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KR20200004562A (ko) 2018-07-04 2020-01-14 한국해양대학교 산학협력단 감귤껍질을 포함하는 전복용 배합사료 조성물

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US4726664A (en) * 1985-03-25 1988-02-23 Nippon Sheet Glass Co., Ltd. Electrochromic device
US4750816A (en) * 1985-05-01 1988-06-14 Toyoda Gosei Co., Ltd. Electrochromic element comprising an organic, oxidative color-forming layer and an inorganic, reductive color-forming layer
US4784477A (en) * 1986-07-22 1988-11-15 Nissan Motor Co., Ltd. Electrochromic device using transition metal oxide and method of producing same
US4983957A (en) * 1987-05-29 1991-01-08 Nissan Motor Co., Ltd. Electrochromic display device capable of display in plural colors
US4960323A (en) * 1988-10-05 1990-10-02 Ford Motor Company Method for maintaining the electrochromic activity of an electrochromic material
US5457564A (en) * 1990-02-26 1995-10-10 Molecular Displays, Inc. Complementary surface confined polymer electrochromic materials, systems, and methods of fabrication therefor
US5818636A (en) * 1990-02-26 1998-10-06 Molecular Displays, Inc. Complementary surface confined polmer electrochromic materials, systems, and methods of fabrication therefor
US5215821A (en) * 1990-12-26 1993-06-01 Ppg Industries, Inc. Solid-state electrochromic device with proton-conducting polymer electrolyte and Prussian blue counterelectrode
AU664766B2 (en) * 1990-12-26 1995-11-30 Ppg Industries Ohio, Inc. Solid-state electrochromic device with proton-conducting polymer electrolyte
KR100392977B1 (ko) * 1994-11-11 2003-10-23 소니 가부시끼 가이샤 광학장치
US6246508B1 (en) * 1996-08-08 2001-06-12 Danionics A/S High voltage electrochromic device
US5774255A (en) * 1996-09-23 1998-06-30 Mcdonnell Douglas Corporation Adaptive infrared modulator
US20050237594A1 (en) * 2004-04-26 2005-10-27 Kuo-Chuan Ho Electrochromic device using poly(3,4-ethylenedioxythiophene) and derivatives thereof
US7342708B2 (en) 2004-04-26 2008-03-11 Tropics Enterprise Co. Ltd. Electrochromic device using poly(3,4-ethylenedioxythiophene) and derivatives thereof
KR20110106622A (ko) * 2010-03-23 2011-09-29 삼성전자주식회사 전기 변색 물질 및 이를 포함하는 전기 변색 소자
US20110235151A1 (en) * 2010-03-23 2011-09-29 Samsung Electronics Co., Ltd. Electrochromic material and electrochromic device including the same
US8947756B2 (en) * 2010-03-23 2015-02-03 Samsung Electronics Co., Ltd. Electrochromic material and electrochromic device including the same
CN102103297A (zh) * 2011-01-14 2011-06-22 天津大学 自褪色节能电致变色器件的制备方法
US11513410B2 (en) * 2017-05-10 2022-11-29 National Institute For Materials Science Electrochromic device using organic/metal hybrid polymer and method for producing same
CN112534344A (zh) * 2018-03-16 2021-03-19 国立研究开发法人物质·材料研究机构 金属配合物系电致变色器件
CN113495392A (zh) * 2020-04-01 2021-10-12 深圳市光羿科技有限公司 一种电致变色器件及其变色方法
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CN112305829B (zh) * 2020-11-13 2022-05-24 烟台大学 一种电致变色玻璃器件的制备方法及应用

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GB2148524A (en) 1985-05-30
GB2148524B (en) 1987-08-05
GB8426631D0 (en) 1984-11-28
DE3438492A1 (de) 1985-05-15
JPS6087316A (ja) 1985-05-17

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